Copolymers of 1-acyloxy-3-buten-2-one



Patented Jan. 5, 1954 COPDLYMERS OF 1-ACYLOXY-3- BUTEN -Z-ONE Joseph M. Wilkinson, Jr., Easton, and John P.. Barker, Media, Pa., assignors to General Aniline New York, N. Y., at (301116.-

&. Film Corporation,

ration of Delaware No-Drawing;- Applicationllecember.20},1950; SerialNo. 201,862

This invention relates; to polymerization of 1'- acyloxy' 3-buten 2 one' with other polymerizable:

unsaturates; As examples of thelatter, there may be mentioned isobutyl' vinyl ether, styrene, vinyl acetate, maleic anhydride, diethyl'fumarate, vinyl chloride, acrylonitrile', methyl methaerylate, etc. However, the compounds mentioned above are not meant to restrictin any way the comonomers whichmay'beemployed, but rather are noted to indicate the wide variety of compounds that are operable.

The 1-acyloxy-3-buten-2 ones are known as a class and are diselosed'in U. S; Patent 2,524,025; they may be preparedas. disclosed in this patent and by other methods. They are illustrated hereinafter by acetoxymethyl vinyl ketone; inasmuch as this material" is readily available and. is. regarded as yielding, products having the widest field of utility;

The preferred l-acyloxy-3-buten-2 ones, which we employ in accordance with the present. invention, are those in, which the acyl group corresponds to that of a saturated monocarboxylic acidv selected. from group consisting, of acetic, propionic; butyricg, isobutyric, Valerie, capric, lauric, myristic, palmitic" and stearic acids.

These copolymerizations' may be carried out with or Without" a. solvent in the presence of a peroxide type or'Friedel-Crafts catalyst or ultraviolet radiation and preferably in an inlet atmosphere, such as nitrogen, within the temperature range of50 Ci to11'00'C; The polymerization may be carried outatatmospheric or superatmospheric pressure depending upon the conditions and thenature of the comonomer employed.

Depending upon the comonomer employed and the reaction conditions, thepolymeric. products vary in consistency, from. t'ough, el'astomerie ma.- terialst'o brittle" solids. Such products fi'ndi particular application. inpressuresensitive adhesives, molding powder, laminates,,textile and leather finishing agents, sheeting, paper fillers, etc.

It, will. be understood. that, the copolymersmay contain other additives, suchas other polymers or copolymers, plasticizers, fillers; pigments, solvents, etc., as? will be understood: byv those skilled in the art. The-properties of the'=-ketone and-"the other polymerizable unsaturate: or mixture of unsaturate may be varied widely: For example, parts of the ketone may be combined with from 1 to 100 parts of the other unsaturate, and the ratio is preferably 2 parts of the ketone to one part of the other unsaturate.

The following examples are illustrative of preferred embodiments of the invention, but substitutions and variations may be made withinthe scope of the claims:

EXAMPLE 1v Into a. reactor were. charged: 19.2; parts by" weight of acetoxymethyl vinyl ketone 15.0.. parts:

of. isobutyl vinyl ether (freshly distilledover-KOH pellets) and 0.68 part technical lauroyl peroxides (Alperox C). After one-half hour in a 60 C. oven, a vigorous reaction took place giving a tough, cream-colored copolymer'which was dissolved in acetone and reprecipitated in diethyl ether. The copolymer was then dried to constant weight by vacuum. A yield of 8 parts (25% of theoretical) of a tough, porous,.white copolymer was found.

Analysis i Found, percent Calculated, percent C 63113" 58.54 H 8.83. 7. 9D.

A reactor was charged with the following 192 Analysis Calculated; Found, percent percent m =0.3= EXAMPLE 3 A: reactor was charged with: 1912' parts by weight of acetoxymethyl vinyl ketone; 12.9 parts of vinyl acetate (freshly distilled) and 0.64 part of technical lauroyl peroxide (Alperox C). After 15 minutes in a C. oil bath, the monomers started reacting violently leaving a light yellow mass which was reprecipitated in hexane from acetone. A yield of 21 parts (66% of theoretical) of tough, white, porous copolymer was gotten.

Analysis Calculated, percent Found, percent n.p=0.42 I

EXAMPLE 4 Analysis Calculated, Found, percent percent EXAMPLE 5 The following were charged into a reactor: 19.2 parts by weight of acetoxymethyl vinyl ketone; 25.8 parts of diethyl fumarate (Eastman Kodak) and 0.90 part of technical lauroyl peroxide (Alperox C). After one-half hour in a 60 C. oven, a vigorous reaction took place giving a copolymer which, when reprecipitated from acetone into hexane, we got a tough, white, porous copolymer. The yield was 9 parts or 20% of theory.

Analysis Calculated, Found, percent percent EXAMPLE 6 Into a reactor was charged: 19.2 parts by weight of acetoxyrnethyl vinyl ketone; 8.0 parts of acrylonitrile (freshly distilled); and 0.54 part of technical lauroyl peroxide (Alperox C.). These monomers after one-half hour in a 60 C. oven reacted vigorously giving a copolymer which, when reprecipitated from N,N-dimethyl form- 4 amide into hexane, was tough and white in color. The yield was 15 parts or of theory.

Analysis Calculated, percent Zhio u u u no: once:

11.,,=0.4a EXAIVIPLE '7 A reactor was charged with: 19.2 parts by weight of acetoxymethyl vinyl ketone; 15.0 parts of methyl methacrylate (freshly distilled); and 0.68 part of technical lauroyl peroxide (Alperox C). The bottle was placed in a C. oven and in one-half hour a vigorous reaction had taken place. A cream, crude polymer was formed and this was reprecipitated from acetone into C014 giving 17 parts (50% of theory) of tough, fiakey, colorless copolymer.

Analysis Calculated, Found, percent percent We claim: 1. A copolymer comprising 10 parts of 1- acyloXy-3-buten-2-one, in which the acyl group.

corresponds to that of a, saturated monocarboxylic acid selected from the group consisting of acetic, propionic, butyric, isobutyric, valeric,v

capric, lauric, myristic, palmitic and stearic acids, and 1 to parts of a polymerizable unsaturated compound selected from the group consisting of vinyl acetate, vinyl chloride, isobutyl vinyl ether,.

maleic anhydride, diethyl fumarate, acrylonitrile, and methyl methacrylate.

2. A copolymer comprising 2 parts of acetoxymethyl viny1 ketone and 1 part of isobutyl vinylv ether.

3. A copolymer comprising 2 parts of acetoxymethyl vinyl ketone and 1 part of styrene.

4. A copolymer comprising 2 parts of acetoxymethyl vinyl ketone and 1 part of vinyl acetate.

5. A copolymer comprising 2 parts of acetoxymethyl vinyl ketone and 1 part of diethyl fumarate.

6. A copolymer comprising 2 parts of acetoxy-.

methyl vinyl ketone and 1 part of maleic anhydride.

JOSEPH WILKINSON, JR. JOHN P. BARKER.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,055,456 Eichwald Sept. 22, 1936 2,484,501 Hagemeyer Oct. 11. 1949 2,524,025 Wilkinson Sept. 26, 1950 

1. A COPOLYMER COMPRISING 10 PARTS OF 1ACYLOXY-3-BUTEN-2-ONE, IN WHICH THE ACYL GROUP CORRESPONDS TO THAT OF A SATURATED MONOCARBOXYLIIC ACID SELECTED FROM THE GROUP CONSISTING OF ACETIC, PROPIONIC, BUTYRIC, ISOBUTYRIC, VALERIC, CAPRIC, LAURIC, MYRISTIC, PALMITIC AND STEARIC ACIDS, AND 1 TO 100 PARTS OF A POLYMERIZABLE UNSATURATED COMPOUND SELECTED FROM THE GROUP CONSISTING OF VINYL ACETATE, VINYL CHLORIDE, ISOBUTYL VINYL ETHER, MALEIC ANHYDRIDE, DIETHYL FUMARATE, ACRYLONITRILE, AND METHYL METHACRYLATE. 